DE2841033A1 - METHOD FOR PRODUCING AQUEOUS POLYMER DISPERSIONS - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk central area

Central area * n c «n« rco

Patents, trademarks and licenses Fr-by 1 ¹ I. οθρ, lif / ö

Process for the preparation of aqueous polymer dispersions

The invention relates to a process for the preparation of polymer dispersions with the aid of new azo-diisobutyric acid (N, N'-hydroxyalkyl) amidines or their salts as water-soluble polymerization initiators and the use of the polymer dispersions obtained as aqueous coating agents in combination with products containing methylol or methylol ether groups or in the production of aqueous coating agents.

From US Pat. No. 2,599,299 it is known to produce the dihydrochloride of azo-di-isobutyric acid amidine.

From DE-AS 1 693 164 it is also known to also produce the acid-free azo-di-isobutyric acid amidine, wherein however, special precautions must be taken must so that the water-moist product does not decompose.

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Also the use of these compounds as polymerization initiators has already been described (see US Pat. No. 2,599,300). However, they failed because of the instability of the initiators themselves as well as because of the corrosion and coagulation problems that occur when using them as initiators, technically not yet used. For this purpose, in particular, the hydrolysis of the free amidine group, which leads to Ammonia, amide groups and ammonium salt groups are responsible for:

RC = - * ■ NH ₃ + R-C "- * - RC NH ₄ ⁺

'MI ₉ NH ₂ O -

R - remainder de? Initiator molecule

While namely the water solubility of the radical formers mentioned a very desirable property per se for polymerization in aqueous suspensions or emulsions represents, the occurrence of salts disrupts the course of the polymerization in many cases. For sensitive emulsions this can lead to premature, undesired coagulation of the emulsions. On the other hand, bothers in many cases also the incorporation of salt-like groups into the polymer and can have a very detrimental effect on their properties.

Surprisingly, it has now been found that through Use of the new azo-di-isobutyric acid (N, N'-hydroxyalkyl) amidines of formula (I)

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HO-R-Nx CH, CH, .NR-OH
CCN = NC-CC

HO-R ¹ -N CH, CH, NR ¹ -OH

X X

in which

R and R ^{1 represent} linear or branched alkylene radicals with 2 to carbon atoms and

X is hydrogen or -R ¹ -OH,

as a polymerization initiator avoids the above-mentioned disadvantages. In addition, polymers are obtained which have very special and desired properties due to the incorporation of the hydrophilic hydroxyalkyl groups.

In formula '(I), R and R ^{1 are} preferably linear or branched alkylene radicals having 2 to 3 carbon atoms, such as -CH ~ -CHj; -CH ₂ -CH ₂ -CH ₂ - or CH ₃

and X is hydrogen or R'-OH.

In particular, in formula (I) R = R ¹ , R and R 'are a linear alkylene radical having 2 carbon atoms (= ethylene radical) and X is hydrogen or β-hydroxyethyl.

The azo-di-isobutyric acid- (N, N'-hydroxialkyl) -amidines of the formula (I) are the subject of the invention, as are their use as radical formers for polymerization processes of unsaturated compounds and / or crosslinking processes of polyunsaturated polymerizable compounds.

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The azo-di-isobutyric acid- (N, N'-bis-hydroxyalkyl) -amidines and azo-di-isobutyric acid- (N, N ¹ -tris-hydroxyalkyl) -amidines can be prepared in that one

A) Azo-di-isobutyric acid arid in which is unsubstituted on the N atoms or substituted on the N atoms by one to five hydroxyalkyl radicals with 2-4 C atoms Ainidine reacts with alkylene oxides (C- - C.) or

B) Azo-di-isobutyric acid iminoalkyl ethers of the general Formula (II) is reacted with monoalkanolamines or mixtures of monoalkanolamines and di-alkanolamines.

CH-, CH

C-C-N-N-C-C ^ (II)

/ · Ι ι \
RO CH ₃ CH ₃ OR

In formula (II), R denotes lower alkyl radicals having 1-4 carbon atoms.

An example is the implementation of azo-di-isobutyric acidiiainoir.ethy 1 ether with monoethanolamine / formula scheme (Illajy and the implementation of azo-di-isobutyric acid iminoethyl ether with a mixture of mono- and diethanolamine ^ formula scheme described:

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(HIa)

EX CK- CH- SH

^S CCNNiC + k NH ₂ -CH ₂ -CH ₂ -OH

CK-O 'CH- OCH-

3 n y> y

HO-CH ₂ -CH ₂ -N j 3 j 3 _y N-CH ₂ -CH ₂ -OH

'C-C-X-N-C-C + 2 XH- + 2 CH-OH

EO-CII ₀ -CH ₀ -N ^ L · L N-CH ₀ -CH ₀ -OH ^{2 2} H ^CH 3, «3 H- ²

(HIb)

^ ^H 3 ^ ^H 3 NH ^ CH ₂ -CH ₂ -OH

CCX = NCC ^ + 2 NH ₂ -CH ₂ -CH ₂ -OH + 2 HX

CH-CH ₃ ^OC 2 ^H 5 ^N CH ₂ -CH _o -0H

KO-CH ₀ -CH ₀ -X ^ I * * I ^ ^ X-CH ₂ -CH ₂ -OH

- ^ CC-NmN-C-CΓ + 2 NH, + 2 C _ft H ₌ -0H

HO-CH ₀ -CH ₀ -N "1 I j ₀

V CII- CII- \

KO-CH ₂ -CH ₂ ^J ^ CH ₂ -CH ₂ -OH

t. ί

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- STILS is easily possible / azo-di-isobutyric acid- (Ν, Ν ¹ -bis- or Ν, Ν'-tris-hydroxialkyl) amidines by first reacting azo-di-isobutyric acid amidine partially with an alkylene oxide and then condensed with mono- and / or dialkanolainin to the desired degree of substitution or the reverse order is chosen. On the other hand, the imino groups of the azo-di-isobutyric acid iminoalkyl ethers can first be fully or partially reacted with an alkylene oxide and then the alkyl ether groups and optionally remaining imino groups with mono- and / or dialkanolamine up to N, N'-bis (hydroxyalkyl) - or . N, N ", N ¹ -Tris- (hydroxyalkyl) amidium of azo-di-isobutyric acid are condensed.

The azo-di-isobutyric acid (Ν, Ν'-bis- or N, N ', N'-tris-hydroxyalkyl) amidines by reaction the azo-di-isobutyric acid iminoalkyl ether with monoalkanolamines or with mixtures of monoalkanol and dialkanolamines (molar ratio 1: 1).

The addition reaction with the alkylene oxides or the condensation with mono- and / or dialkanolamine takes place at 0-50 ° C, preferably 20-45 C. The reactions can solvent-free or in the presence of organic solvents under the test conditions are indifferent to the reactants, for example in alcohols such as methanol, ethanol, in Ethers such as diethyl ether or dioxane; in ketones such as acetone or ethyl methyl ketone, but also in aliphatic ones

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or aromatic hydrocarbons. The reactions can be carried out without pressure or under pressures of up to 50 bar will.

Suitable alkylene oxides are: ethylene oxide, propylene oxide, 1,2-epoxy butane, 2,3-epoxy butane, 1,2-epoxy-2-methylpropane, preferably ethylene oxide and propylene oxide, especially ethylene oxide.

The following can be used for the reaction with the iminoalkyl ethers: ethanolamine, diethanolamine, 1-amino-propanol- (2), Bis (2-hydroxypropyl) amine; 1-amino-propanol- (3), bis- (3-hydroxypropyl) -amine; Isopropanolamine, diisopropanolamine; 1-amino-butanol (4), bis- (4-hydroxy-butyl) amine; 1-amino-butanol- (3), bis- (3-hydroxy-butyl) amine; 1-amino-butanol- (2), bis- (2-hydroxy-butyl) amine; 1-amino-2-methyl-propanol- (2), Bis (2-hydroxy-2-methyl-propyl) amine; 2-amino-2-methyl-propanol- (1), bis- (monohydroxitert.-butyl) amine; i-Amino-2-methyl-propanol- (3) and bis- (3-hydroxy-2-methyl-propyl) -amine or mixtures of the aforementioned amines.

The following are preferably used: ethanolamine, diethanolamine, 1-amino-propanol- (2), bis- (2-hydroxypropyl) -amine, 1-amino-propanol (3), Bis (3-hydroxypropyl) amine, isopropanolamine, diisopropanolamine or their mixtures, in particular ethanolamine or diethanolamine or mixtures thereof.

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The alkylene oxides are preferably used in such amounts used that on an imino group of the amidines or Imino ethers account for about 1 mole and an amino group of the amidines accounts for about 2 moles of alkene oxide. Of the alkanolamines or Dialkanolamines preferably get 1 mol per imino, amino or alkyl ether group of the amidines or imino ethers for use.

The reaction of iminoalkyl ethers with amines to form amidines is known in principle from the literature (cf. methods of organic Chemie, Houben-Weyl, 4th edition, (1952) Volume 8, page 703); likewise the hydroxy alkylation of amidines with alkylene oxides (cf. US Pat. No. 2,980,554, column 3, lines 41-43).

The preparation of the azo-di-isobutyric acid iminoalkyl ether used as starting materials is also known and can be carried out, for example, according to the method of DE-OS 2 242 520 (pages 31-32).

Of the azo-di-isobutyric acid (Ν, Ν'-hydroxialkyl) amidines prepared by the process discussed named for example:

Azo-di-isobutyric acid (N, N ^r -bis-2-hydroxiethyl) -amidine, azo-di-isobutyric acid- (N, N'-bis-3-hydroxipropyl) -ainidine, azo-di-isobutyric acid- (N, N'-bis-2-hydroxypropyl) -amidine, azo-di-isobutyric acid- (N-2-hydroxiethyl-N'-3-hydroxypropyl) -amidim

Azo-di-isobutyric acid- (N-2-hydroxiethyl-N'-2-hydroxipropyl) -amidine,

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Azo-di-isobutyric acid (N, N ¹ -bis-3-hydroxibutyl) -amidine, azo-di-isobutyric acid- (N, N ', N'-tris-2-hydroxiethyl) -amidine, azo-di-isobutyric acid - (N, N ¹ , N'-tris-3-hydroxipropyl) -amidine, azo-di-isobutyric acid- (N, N ', N'-tris-2-hydroxipropyl) -amidine, azo-di-isobutyric acid- ( N-2-hydroxiethyl-N ¹ , N'-bis-3-hydroxipropyl) -amidine,

Azo-di-isobutyric acid- (N-2-hydroxiethyl-N ', N'-bis-2-hydroxipropyl) -amidine,

Azo-di-isobutyric acid- (N-3-hydroxipropyl-N ¹ , N'-bis-2-hydroxyethyl) -amidine,

Azi-di-isobutyric acid- (N-2-hydroxipropyl-N ¹ , N'-bis-2-hydroxiethyl) -amidine,

Azo-di-isobutyric acid (N-2-hydroxypropyl-N ¹ , N'-bis-2-hydroxiethyl) amidine.

^{The azo-di-isobutyric acid (N, N 1} -hydroxialkyl) amidines obtained under the specified reaction conditions in smooth reaction and good yields are water-soluble, yellow to yellow-orange-colored oils. They can be used as radical formers in the polymerization of unsaturated compounds. They can also be used in crosslinking processes of or with unsaturated compounds or products, optionally with foaming. They can also be used as blowing agents in the production of foams.

In the following and in Examples 7 to 19, the use of azo-di-isobutyric acid (N, N ¹ -hydroxialkyl) amidines in the preparation of aqueous polymer dispersions is described.

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Polymer dispersions are widely used as coating material or in combination with pigments and fillers, as coatings for wood, metal, plastics, ceramics and the like. Manufactured. For one The coatings adhere well to the substrate, even in a humid atmosphere or in the presence of water it is important that the content of water-soluble salts in a polymer film is as low as possible.

The salts not only worsen the adhesion of the films to the substrate, but also the Film dissolution favored from the surface. This is particularly critical when the polymer is hard and not very sticky; small amounts of salt then particularly disturb the coalescence of the latex particles sensitive. When exposed to water, osmotic reactions occur at the diffusion interfaces of the latex particles Apply pressure through the dissolving salts, which whiten the binder and soften it can lead to dissolution.

It has therefore been suggested to use hydrogen peroxide or water-soluble, non-salt-like derivatives of perhydrol like tert. Polymerize butyl hydroperoxide. However, these latices show poor ion and shear stability. Furthermore, it has often been suggested to polymerize with very small amounts of persulfates. this however, leads to poorly reproducible approaches, which

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if necessary be able to coagulate completely.

It has now been found that polymer dispersions without the aid of inorganic ones can improve adhesion and water resistance of the polymers can produce worsening salts if one is used as the polymerization initiator instead of the usual alkali or ammonium persulfates or other salt-like peroxy compounds, azo-di-isobutyric acid (N, N'-hydroxyalkyl) amidines of formula I used.

These represent a valuable addition to the already known water-soluble iX, ck '-azo- (o <-methyl- * f -sulfo) -butyric acid dinitrile (IV) (cf. DE-AS 1 111 395), to the azodinitriles from Type of oC, <X'-Azo- ( OC -methy1- ^ - diethylamino) -butyric acid dinitrile (V) (see US Pat. No. 2,605,260), to the type of ^ -, ^ - '-Azo- ( f -cyan) -valeric acid = · «(, oC ¹ -Azo- (o (-methyl- fr -sulfo) -butyric acid dinitrile (VI) (cf. US Pat. No. 2,520,338) or finally on 2.2 '-Azo- (2-methyl-propion-amidine), (VII), (see U.S. Patents 2,599,299 and 2,599,300).

CH ₃ CH ₃
HO ₃ S-CH ₂ -CH ₂ -CN = NC-CH ₂ -Ch ₂ -SO ₃ H (IV)

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Al

^C 2 ^H 5 ^C 2 ^H 5

.N-CH ₉ -CH ₀ -CN = NC-CH ₀ -CH ₀ -N (V)

_r "/ C = NC = N \

C ₂ H ₅ C ₂ H ₅

CH ₁ CH-,

HOOC-CH ₂ -Ch ₂ -CN = NC-CH ₂ -CH ₂ -COOH (VI)

C = N C = N

C-C-N = N-C-C (VII)

The amidines rom type (VII) are generally used as hydrochloric acid salts (cf. US Pat. No. 2,599,300). However, these must be used in an ice-cold state in order to avoid undesired decomposition or hydrolysis, (see example for the production of a polyethylene latex with the amidine of an azodinitrile in: Houben-Weyl, "Methods of Organic Chemistry, 4th Edition, Volume XIV / 1 (1961), page 222 ff). Chloride ions, however, have a particularly disadvantageous effect in a latex intended for the corrosion protection sector, since they strongly accelerate the formation of rust. In addition, the amidines of type (VII) can only have a beneficial effect in a neutral or acidic formulation unfold.

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- ys -

In contrast, the initiators according to the invention are the Formula (I) stable in aqueous solution at room temperature. They work in both acidic and alkaline medium and are extremely soluble in water.

The compounds of type (VI) are only alkaline or neutrally soluble and for monomers, which are preferred are to be polymerized in an acidic or weakly acidic medium, poorly suited.

Compared to the compounds of type (V), those according to the invention show Initiators have a significant advantage: they have free OH groups in the molecule, which at the beginning and end of a polymer chain are incorporated. These OH groups impart improved adhesion and are accessible as reactive groups for crosslinking reactions and desirable for many purposes.

The compounds of type (IV) lead to stable latices; the sulfo groups then introduced into the polymer, on the other hand, worsen the water resistance of the films which can be produced from such dispersions. In addition, the acidic groups must be the initiators. Type (IV) can be buffered again with bases so that it ultimately has no particular advantages over the otherwise customary potassium or ammonium persulfate.

The initiators / the formula (I) according to the invention can be used in an alkaline, but also in an acidic medium

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· You are already feeding in low doses high polymer yields, as can be seen from the examples.

It has proven to be particularly advantageous to use the initiators of the formula (I) as salts or adducts polymerizable.r To use acids. By this measure, the polymerization can be carried out at any pH value from about 3-9 will. Examples of polymerizable acids are monoolefinically unsaturated carboxylic acids 3-5 carbon atoms named such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid / furthermore are maleic acid half esters, Itaconic acid half-esters, fumaric acid half-esters each with 1-18 carbon atoms in the alcohol component are suitable. If appropriate, “vinylsulfonic acid, methallylsulfonic acid or 2-N-acrylamido-2-methyl-propanesulfonic acid are also used Can be used for pH adjustment when the electrolyte stability of the dispersions is in the foreground of wishes.

The alkaline reaction of the initiators of the formula (I) can finally also be achieved by adding alkyl sulfonic acids and / or alkylaryl sulfonic acids are reduced, with Salts with emulsifier properties are formed. Also aliphatic Monocarboxylic acids can be used to advantage.

The polymerization with the initiators of the formula (I) is preferably carried out in the temperature range from 50 ° -90 ° C.

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in particular between 50 ° and 80 ⁰ C and at zero pressure or at pressures up to 200 bar.

The initiators can be used in amounts of 0.2-10% by weight, based on total monomers. In general, amounts of 0/3-2% by weight are used. If one attaches importance to an increased incorporation of hydroxyl groups as well as to a low molecular weight, then correspondingly higher amounts are used.

The initiators can be used in various ways during the polymerization Way to be admitted. The amount of initiator can be metered in linear fashion at a speed which just compensates for the decomposition of the initiators at the respective polymerization temperature. However, it is also possible to initially charge the entire initiator or to add the main amount only to the last monomer fractions. Depending on the type of initiator metering, products of different molecular weight distributions are formed and different properties.

In the case of dispersions which are to be used as binders for the production of aqueous fire finishes , it is advantageous, for example, to add most of the OH group-containing initiators of the formula (I) only towards the end of the monomer feed, so that initially high molecular weight, low hydroxyl groups, towards the end of the Polynerization, on the other hand, low molecular weight, the flow and gloss

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improving polymer fractions which, due to their higher hydroxyl end group fraction, can be crosslinked with formaldehyde resins develop.

It has now been found, surprisingly, that the stability of the initiators produced with the initiators according to the invention Polymer dispersions is very good, even if anionic emulsifiers are used, although in usually when incorporating cationic groups into a polymer in the presence of anionic emulsifiers with flocculation is to be expected.

In addition to the polymerization initiators according to the invention, it is therefore possible to use the customary emulsifiers of the anionic, nonionic or cationic classes. Customary cationic, anionic or nonionic emulsifiers are described, for example, in Methods of Organic Chemistry, Houben-Weyl, 4th edition (1961), volume XIV / 1, pages 190-208 and the same manual 4th edition (1959) volume II / 2 , Pages 113-138 and AM Schwartz and JW Perry, Surface Active Agents, Interscience Publ. Inc., New York, 1958, pages 25 to 171.

Also combinations of anionic with non-ionic in a ratio of 7: 3 to 3: 7 (molar ratio) or equivalent Combinations of cationic and non-ionic emulsifiers are possible.

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However, the polymerization can also be carried out without the aid of customary emulsifiers if compounds are used used, which form emulsifier-like oligomers or a dual function as an emulsifier and play monomers.

Such substances are, for example, alkali or ammonium or. Amine salts of the maleic acid half esters with an alcohol residue, which has more than 5 carbon atoms, for example cyclohexyl maleic acid-maleic acid dodecyl half-ester salts. However, the polymerization can also be carried out in the absence of emulsifiers with the aid of protective colloids, such as for example polyvinyl alcohol.

Polymerizable monomers are all otherwise customary unsaturated monomers polymerizable with azodiisobutyric acid nitrile in non-aqueous solution into consideration, for example styrene, Oi-MethyIstyrol. Butadiene, acrylic acid ester with 1-8 carbon atoms in the alcohol component, Methacrylic acid esters with 1-8 carbon atoms in the alcohol component, acrylonitrile, methacrylonitrile, vinyl chloride, Vinyl acetate, ethylene, chloroprene, etc.

In addition to the monomers mentioned, in addition, to a lesser extent Proportion, water-soluble compounds such as methacrylic acid, acrylic acid, maleic acid half-esters, itaconic acid and Itaconic acid half esters, acrylamide, methacrylamide, etc. are polymerized. Furthermore, functional parts

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Groups, e.g. comonomers bearing OH or epoxy groups can also be used, such as ß-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate and N-methylol or N-methylol alkyl ethers of (meth) acrylic acid amide.

The polymer dispersions can be used in many ways. Examples 7-19 serve to illustrate the Mode of action of the new initiators and should in no way limit the possibility of use.

If the dispersions described are film-forming, they are extremely suitable for coatings, especially for those with an increased anti-corrosive effect, an improved salt spray test, a good one Adhesion, improved compatibility and crosslinking with methylol or methylol ether groups Products, for example, with aminoplasts such as melamine-formaldehyde resins or urea-formaldehyde resins or Phenoplasts such as resols are required.

In this application, the term polymers includes homopolymers and copolymers. Copolymers are not just Copolymers with a statistical distribution of the polymerized monomers understood or block copolymers, but also graft copolymers in which monomers are grafted onto a preformed homopolymer or copolymer have been. Of the copolymers, random copolymers are preferred.

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- ur -

Azo-di-isobutyric acid (N, N'-hydroxyalkyl) amidines are also used of formula (I) excellently suitable for the polymerization in the homogeneous phase, which is known per se. This is preferably understood to mean the polymerization in solution and in substance. The polymerization can, however also only start in the homogeneous phase and the polymer during the polymerization (precipitation polymerization) incurred in finely divided form.

Practically all olefinically unsaturated monomers, which are suitable for the polymerization with radical-forming azo compounds. For example are mentioned:

a) »X \, ß-monoolefins with 2-8 carbon atoms, such as ethylene, Propylene, butene-1, isobutylene, diisobutylene;

b) Conjugated diolefins with 4-6 carbon atoms, such as butadiene, isoprene, 2,3-dimethylbutadiene, 2-chlorobutadiene, preferably Butadiene;

c) (Meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid amide, (Meth) acrylic acid alkyl esters with 1-18, preferably 1-8 carbon atoms in the alcohol component, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate or the corresponding Methacrylic acid alkyl esters, preferably

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- ac -

Acrylic acid, acrylonitrile, acrylamide, methacrylate, butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, Methyl methacrylate;

d) Vinyl esters of organic monocarboxylic acids, the acid component having 1-18, preferably 2-4, carbon atoms contains, such as vinyl acetate "and vinyl propionate, vinyl acetate is preferred;

e) monoolefinically unsaturated halogenated hydrocarbons, such as vinyl chloride or vinylidene chloride, preferably vinyl chloride;

f) vinyl aromatics such as styrene, o- or p-methylstyrene,

OC-methylstyrene, θί-methyl-p-isopropylstyrene, ° 6 -methylm-isopropylstyrene, p-chlorostyrene, preferably styrene.

The monomers that are less prone to polymerization, such as oC -methylstyrene and m- or p-isopropyl- (X-methylstyrene, are preferably always used in a mixture with at least one further of the specified copolymerizable monomers.

g) Monoesters of ο ^, β-monoolefinically unsaturated monocarboxylic acids with 3-4 carbon atoms with dihydric saturated aliphatic alcohols with 2-4 carbon atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate _f 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate;

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h) N-methylol ethers of acrylic acid and methacrylic acid amide of the general formula VIII

CH ₂ = C - CO - N - CH ₂ - OR _{2 (γΐΙΙ)}

RR ₁

in the
R for hydrogen or methyl,

R _{1 represents} hydrogen, alkyl, aralkyl or aryl,

R_ for alkyl or cycloalkyl, such as methyl, ethyl, n-propyl, Isopropyl, η-butyl, isobutyl, cyclohexyl are available (see German Auslegeschrift 1 035 363).

N-methylol methyl ether of methacrylic acid amide is preferred. The monomers of group h) are used in amounts of 1-20% by weight, based on total monomers, and are incorporated into the copolymer ;

i) Di- and monoesters of oC, ß-monoolefinically unsaturated dicarboxylic acids containing 3-5 C atoms, such as maleic, fumaric and itaconic acid, with 1-18 C atoms in the alcohol component, also maleic anhydride, maleic or fumaric acid, amides of maleic and fumaric acid, maleimides and unsaturated copolymerizable polyesters, which are the radicals as polymerizable constituents

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of maleic and / or fumaric acid. Maleic anhydride is preferred;

j) vinyl alkyl ethers with 1-4 carbon atoms in the alkyl group, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, Vinyl butyl ether.

k) Crosslinking monomers with several nonconjugated ones olefinically unsaturated carbon-carbon bonds, such as divinylbenzene, diallyl phthalate, Divinyl adipate, acrylic and / or methacrylic acid allyl ester, methylenebisacrylamide, methylenebismethacrylamide, Triallyl cyanurate, triallyl isocyanurate, triacryloyl perhydro-S-triazine, bisacrylates or bis-methacrylates of glycols or polyglycols "with 2-20 carbon atoms, such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Butylene glycol 1,4-di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Tris (meth) acrylates of trimethylolpropane or glycerol.

The crosslinking monomers of group k) are preferably used in amounts of 0.1-12% by weight, based on total monomers, used for copolymerization. They are incorporated into the copolymer in equal proportions.

In addition, primary, secondary or tertiary aminoalkyl esters of (meth) acrylic acid with preferably 2-4 C atoms in the alkyl group and glycid (meth) acrylate as Comonomers are used and optionally via the

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Amino or epoxy group during or after the copolymerization be networked.

Preference is given to monomers of groups b), c), d), e), f) and i) used for co-polymerization.

When polymerizing in solution, water and organic solvents / for example dimethylformamide, tert-butanol, chlorobenzenes, etc. are used.

The polymerization can be carried out according to the disintegration characteristics of the azo compounds according to the invention between 50 ° C

and 90 ° C, preferably 55 ° C-75 ° C. The amount . of the initiator can be adapted to the desired molecular weight and between 0.05 to 10 and more wt .-% of the monomers used. Of course, this information on the amount of initiator and temperature can be used can also be deviated from. The polymerizations in the homogeneous phase can be pressureless or at pressures up to 1500 bar can be carried out.

The polymers obtained contain at least two hydroxyl groups incorporated at the beginning and end of each polymer chain, originating from the initiator fragments.

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The introduction of hydroxyl groups at the beginning and end of polymer chains are of great practical importance for the various properties; once they may be due to their ability to react with compounds umgasetz t react with hydroxyl groups and generally form wide-meshed networks. Such compounds are, for example, polyisocyanates, polyepoxides, polycarboxylic anhydride, compounds containing methylol and / or methylol ether groups. In addition, due to the hydroxyl groups, the adhesion of polymer films is considerably improved.

Examples 20-27 explain bulk and solution polymerization using the azo-di-isobutyric acid (N, N'-hydroxyalkyl) amidines of the formula T.

The parts and percentages given in the examples relate to weight, unless already stated. The limiting viscosity number (intrinsic viscosity) lP * lJ ', (_ -1 was in the specified solvents

~ ο ~
measured at 25 C.

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Production of azo-di-isobutyric acid (N, N'-hydroxyalkyl) amidines

Example 1; Azo-di-isobutyric acid- (N, N'-bis-2-hydroxiethyl) -amidine

114 g (0.5 mole) of azo-di-isobutyric acid iminomethylether, 300 ml of methanol and 122 g (2 moles) of ethanolamine were stirred at 50 ⁰ C for 8 hours. To remove methanol and ammonia (1 mol), the mixture was distilled out in a water jet vacuum (12 mbar) at temperatures up to a maximum of 50.degree. 165 g = 88.2% of the theory of a yellow-orange-colored, _{water-soluble oil, n D 1.4880, remained.}

Analysis calculated for C ₁₆ H ₃₄ NgO ₄ , molecular weight 374, calculated C: 51.34%; H: 9.09%; N: 22.46%; 0: 17.11% found C: 51.5%? H: 9.3%; N: 22.8%; 0: 17.4 %

Example 2: Azo-di-isobutyric acid- (N, N ', N'-tris-2-hydroxiethyl) -amidine (two-step process)

In 37.4 g (0.1 mol) of the azo-diisobutyric acid obtained according to Example 1 (N, N'-bis-hydroxiethyl) -amidine were cooled with ice water at 20.degree.-30.degree. C., 8.8 g (0.2 mol) of ethylene oxide initiated. The mixture was left at room temperature for 5 hours.

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temperature (approx. 25 ° C) stirred. This gave 46 g = 99% of theory of a yellow, viscous, water-soluble oil, n _D 1.4910.

Analysis calculated for ^C 20 ^H 42 ^N 6 ° F ^{1 M} 19 weight 462 calculated C: 51.95%; H: 9.09%; N: 18.18%; 0: 20.78% found C: 52.2%; H: 9.2%; N: 18.5%; 0: 20.4%

The same azo-di-isobutyric acid- (N, N ¹ , N ¹ -tris-2-hydroxiethyl) -amidine is also obtained by the following procedure of Example 3:

Example 3: Azo-di-isobutyric acid- (N, N ¹ , N ¹ -tris-2-hydroxiethyl) -amidine (one-step process)

45.6 g (0.2 mol) of azo-di-isobutyric acid iminoethyl ether, 200 ml of methanol, 42 g (0.4 mol) of diethanolamine and 26 g (0.4 mol) of ethanolamine were ^{stirred at 50 °} C. for 8 hours. The mixture was distilled to remove methanol and ammonia (0.4 mol) in vacuo (12 mbar) at temperatures up to 50 ⁰ C. 91 g = 98% of the theory of a yellow, viscous, water-soluble oil remained which had the same refractive index as the oil of the previous example and was identical to it.

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Example 4; Azo-di-isobutyric acid- (N, N'-bis-2-hydroxypropyl) -amidine

57 g (0.25 mol) of azo-di-isobutyric acid iminomethyl ether, 200 ml of methanol and 75 g (1 mol) of i-amino-2-propanol

^{were heated to 50 °} C. for 8 hours in a water bath, 0.5 mol of ammonia being released. The mixture was distilled off from the volatile components at 50 ° C., first at 12 mbar, then at 0.1 mbar. The residue left was 93 g = 87% of the theory of a yellowish, water-soluble oil, n ~: 1.4691

Analysis calculated for ^C 2o ^H 42 ^N 6 ° 4 'Molecular weight 430 calculated C: 55.81%; H: 9.76%; N: 19.53%; 0: 14.88 % found C: 56.1%; H: 10.0%; * N: 19.7%; 0: 14.7%

If 1-amino-3-propanol is used instead of 1-amino-2-propanol in the above approach, the azo-di-isobutyric acid (N, N'-bis-3-hydroxypropyl) -amidine is obtained as yellow oil, which solidifies to a yellowish paste when standing.

Example 5; Azo-di-isobutyric acid- (NjN'-bis-S-hydroxi butyl) -amidine

45.6 g (0.2 mol) of azo-di-isobutyric acid iminomethyl ether, 200 ml of methanol and 73.2 g (0.8 mol) of 1-amino-3-butanol

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were heated to 40 ° C. for 8 hours, 0.4 mol of ammonia being released. The mixture was freed from the volatile constituents at 50 ° C., first at 12 mbar, then at 0.1 mbar. The residue remained 91 g = 93% of theory, yellow oil, n ^ ⁰ ; 1.4801

Analysis calculated for Cp ₄ Ht _n N ^ -O., Molecular weight 486, calculated C 59.26%; H: 10.29%; N: 17.28%; 0: 13.13% found C 59.1%; H: 10.5 %; N: 17.4%; 0: 13.6%

Example 6: Azo-di-isobutyric acid- (N-2-hydroxypropyl-N ¹ , N ¹ IQ bis-2-hydroxiethyl) -amidine

128 g (0.5 mol) of azo-di-isobutyric acid iminoethyl ester, 400 ml of methanol, 75 g (1 mol) of 1-amino-2-propanol and 105 g (1 mol) of bis (2-hydroxyethyl) amine were Heated to 50 for 8 hours, releasing 1 mol of ammonia. The mixture was freed from the volatile components at 50 ° C./12 mbar and then at 50 / 0.1 mbar. The residue remained 224 g = 92% of the theory of a yellow, water-soluble oil, n _D °: 1.4780

Analysis calculated for C ₁₀ H., NO 1, molar weight 490, calculated C: 53.88%; H: 9.39%; N: 17.14%; 0: 19.59% found C: 53.6%; H: 9.7%; N: 17.0%; 0: 19.8%

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Application examples 7 to 19 relating to manufacture aqueous Polyitierisatdispers ionen

Example 7

The emulsion polymerization is placed in a 4 l five-necked flask made of Jena glass with a Dimroth reflux condenser Gas bubble counter (with a three-way valve connected between the cooler and the sealing liquid), one with nitrogen water-cooled stirrer equipped with a supply tap (with drive motor and expandable by centrifugal force, stirrer blades offset by 90 ° C), a joint thermometer or a thermometer inserted into the flask. a thermal sensor sleeve.

Two Anschütz attachments, which either have four dropping funnels, are placed on the two remaining ground-joint necks with pressure equalization for dosing the solutions I to IV listed below or carry a dropping funnel for solution I and three inlet nozzles (consisting of a ground-joint cap with a core and a centrally fused, have a dropping glass tube which is bent at the top and fitted with a stopcock. At this lockable inlet connection If necessary, the three mini-dosing pumps become the storage vessels for the solutions or mixtures II, III and IV leading hoses connected.

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The "template" is then filled into the flask Solution. After opening the vessel via the three-way stopcock (at closed taps of the inlet connection and the nitrogen admixture: -. «.?) evacuated, is balanced with nitrogen. By an Lr. the N ^ feed line switched, in water oir.tsuchenc'.os T-Pohr with check valve is an overpressure avoided in the glass flask.

The evacuation and subsequent gassing with N_ takes place 3 times. Then all air is out of the reaction space. repressed. The publishers are now at a slight N_ overpressure (2 bubbles / see.) with stirring (approx. 250 - 300 rpm) to the desired Polymerization temperature, here 70 C, heated.

The flask is immersed in a well-insulated water bath with an overflow, which is heated by an immersion heater τ-> and through a valve, which cold water flows in can be cooled, with the maximum temporal heating rate and maximum cooling rate approximately corresponding.

Immersion heater and cooler are manipulated variables of a control device, the controlled variable of which is the internal temperature (i.e. the Temperature of the dispersion), the disturbance of which is primarily the exothermic reaction.

In this way, the internal temperature can be very accurately to adjust. The setpoint deviation is less than 1 degree with a uniform reaction.

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BATH ORIGINAL

If the desired polymerization temperature is now reached, the solution is added once, after which the polymerization usually starts immediately. As soon as a bluish seed latex is formed and the heat of polymerization subsides, solutions II, III, IV are added dropwise in the course of a certain metering time, here 6 hours odor pumped in via suitable mini-dosers, which is more precise is.

Once all the components have been added, the process is completed of the I``. cr.oii! c-; reriui'isatzes for some time (here 2 hours) post-polymerized at a boötir.mten temperature (here 85 C).

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BATH ORIGINAL

W-

2841Q33

Template:

Parts by weight based on total proponents

Fully desalinated ces or 930.0 33.646 distilled water 6.0 0.217 Sodium lauryl sulfate 64.2 2,323 Acrylo.'iu ro- n-bu Lylc-s ter 17.05 0.617 Acrylonitrile 17.05 0.617 Styrene 4.0 0.144 Methacrylamide

Solution I.

Distilled water
(or vollc ntsalztes-H ₂ O 81 0 azo-di-isobirttersäure- (Μ, Ν ¹ -to-2-hydroxisthyl) -amidin 2.5 methacrylic acid, 50% in water 2.2

2.930

0.090 0.077

Solution II

Aeryl acid n-butyl ester 715.2 25.875 Acrylonitrile 189.9 6.87 Styrene 189.9 6.87 Ilethacrylamide 45.7 1.6533

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BATH ORIGINAL

28A1033

Original g parts by weight based on total components

Solution III

Water (see above) 270.0 9.768 azo-di-isobutyric acid
(N, N'-bis-2-hydroxyethyl) -

anidine 7.0 0.253

Methacrylic acid, 50%

in water 6.2 0.224

Solution IV

Water (supra) 196.0 7.091

Sodium lauryl sulfate 20.2 0.731

Sum, total 2,764.1 <v 100

Polymerization temperature: 70 ° C
Inflow time of II, III, IV 6 hours
Post-polymerization: 2 hours at 85 ° C.

The low-viscosity latex obtained in this way has a solids content of 45-46% and is easy to use pass through a 30, u-cloth made of perlon fabric with square! • flaps, leaving only a little coagulate (approx. 0.5 -5g) remains.

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The latex has uniform particles of approx. 130 nm Diameter. It dries at 25 C to form k films with good water resistance.

Diameter. It dries to clear, tack-free at 25 ° C

A drop of water placed on the film surface leads after approx. 30 minutes no clouding or film dissolution whatsoever. To improve the ion resistance, the latex can be treated with nonionic emulsifiers afterwards be treated afterwards. However, this is only necessary for special applications.

The latex can be mixed with commercially available water-soluble melamine-formaldehyde resins used for stoving enamels or mix urea-formaldehyde resins. Pigments and fillers can also be added to these mixtures can be added. Such aqueous stoving systems show the absence of customary inorganic salts improved water resistance and adhesion on various substrates, especially on metals.

The polymer on which the latex is based is soluble in tetrahydrofuran or dimethylformamide without gel and has an intrinsic viscosity of [_ O2_7 = 3.0 dl / g at 25 ° C. in tetrahydrofuran.

It consists of:

62.7% polymerize butyl acrylate units

16.65% acrylonitrile units

16.65% styrene units

4.0% methacrylamide units

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Example 8: (comparisons)

A) The procedure is as in Example 7, but the initiator is replaced by the same amount of ammonium peroxide sulfate. The resulting, coagulate-free latex is discolored yellow. Clear films made from this latex show one poorer adhesion to glass and greater sensitivity to water. Melamine-formaldehyde-resin mixtures prepared with this latex in an analogous combination with pigments give significantly poorer results when stored in water. The ones branded on metal Layers peel off from the subsurface.

b) Example 7 is repeated with the change that the initiator by the same amount of v-, f'- azo- (Ϋ -cyano) -valeric acid (formula (VI), dissolved in the equivalent amount of dilute, aqueous 10% ammonia solution The latex has a particle size of about 150 nm, is strongly yellow in color and contains about 15 g of coagulate 3O minutes to break up the film.

Example 9

The procedure is as in Example 7, but the initiator is replaced by azo-di-isobutyric acid- (N, N ', N'-tris-2-hydroxyethyl) -

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amidiη. An almost monodisperse latex is obtained properties similar to those described in Example 7

10

In the apparatus described in Example 7, the solution referred to below as "receiver" is poured in and heated to 75 ° C. under nitrogen. After injection of I, the Zuciosierung of II, III and IV takes place in the course of 5 hours, after which the Te
stirred v; ird.

after which the temperature is increased to 80 ° C and 2 hours after

A thin, coagulate-free latex also results a solids content of 46.5%. After removing the The latex can contain residual monomers with water-soluble, commercially available Urea-formaldehyde resins or melamine-formaldehyde resins and pigments can be mixed and used as an aqueous stoving enamel.

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template

LÖEunq I

Distilled water

100.0

Azo-di-isobutyric acid (N, N'-bis-2-hydroxyethyl) -

Parts by weight based on total packages

Distilled water 919.0 31.8971 Sodium Lauryl Sulphate 6.0 0.208 Acrylic acid n-butyl ester 60.0 2.082 Acrylonitrile 15.0 0.5205 Styrene 15.0 0.5205 Methacrylic acid-2-
hydroxypropyl ester 10.0 0.347 Methacrylamide 2.0 0.0694 Methacrylic acid 2.0 0.0694

3.471

aiTiidin 50 % ig 3 , 0 0 , 104 Methacrylic acid in H _? 0 2 , 64 0 , 0916

Solution II

Acrylic acid n-butyl ester 700.0

Acrylonitrile 175.0

Styrene 175.0

Methacrylic acid 2-hydroxy

propyl ester 116.7

.Methacrylamide 23.3

Methacrylic acid 23.3

24.296 6,074 6,074

4.050 0.809 0.809

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28A1033

template

Parts by weight based on total components

Solution III

Distilled water 300.0

Azo-di-isobutyric acid (X, N "' -bis-2-hydroxiethyl) -amidine 7.0

Methacrylic acid, 50%

in water 6.2

10,412

0.243 0.215

Solution IV

Distilled water
Sodium Lauryl Sulphate

200.0 20.0 6.941 0.694

Suirjne, overall

2,881.14 100

Polymerization temperature:
Inflow time of II, III, IV:
Post-polymerized:

75 ° C for 5 h 2 h at 80 ° C

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Since the copolymerization of the monomers took place almost quantitatively as in the following examples, the integral composition of the polymer corresponds to the composition of the monomer mixture:

57.7 C-LW ₁ - ⁹ O Acrylsäurebutylestereinheiten

14.45 wt .- 'i acrylonitrile units

14.45 G2W.-TS styrene units

9.6% by weight, 2-hydroxypropyl methacrylic acid units

1.9 Gow.-S methacrylic acid units

1, 9 Gc -I . -'i methacrylamide units

100% by weight

Example 11

Be in a three-necked flask

400 parts by weight of distilled water 1 part by weight of an alkyl monosulfonate

with 12 to 14 carbon atoms: 0.25 parts by weight of azo-di-isobutyric acid

(N, N'-bis-2-hydroxiethyl) -amidine

presented and heated to 80 ° C.

Then 50 parts by weight of a mixture

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200 parts by weight of styrene

275 parts by weight of n-butyl acrylate 25 parts by weight of methacrylic acid

admitted. After stirring for 30 minutes at 80 C, within 3 hours, the remainder of the monomer mixture and a solution are uniformly dripped out

350 parts by weight of distilled water 10 Gev /. Parts of an alkyl monosulfonate with 12 to

14 carbon atoms and 5 parts by weight of azo-di-isobutyric acid- (Ν, Ν ¹ -bis-

hydroxiethyl) amidine

at 80 ° C. The mixture is then stirred at 80 ° C. for 2 hours. After degassing, 1230 parts by weight of a are obtained Coagulate-free dispersion with a solids content of 39% and an average particle size of 145 nm. The flow time in the DIN cup (2 mm nozzle) is 69 s.

Example 12

Geir.äß Example 11, instead of the monomer mixture specified there, a mixture of

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190 parts by weight of styrene

260 parts by weight of acrylic acid n-butyl ester

25 parts by weight of methacrylic acid and 25 parts by weight of 2-hydroxypropyl methacrylate

used. All other conditions remain unchanged. After degassing, 1.150 parts by weight of a are obtained Coagulate-free dispersion with a solids content of 39.5% and an average particle size of 138 nm.

The flow time in the DIN cup (2 mm nozzle) is 78 s.

The dispersion obtained in this way dries at 25 ° C. to give clear, waterproof films . It can be mixed with melamine-formaldehyde resins or urea-formaldehyde resins and pigments. These mixtures can be stoved onto metals, resulting in well-adhering waterproof and solvent-resistant coatings.

example 13th

According to Example 12, an equivalent amount of azo-di-isobutyric acid (N _f N'-bis-2-hydroxypropyl) aniiain is used as initiator. After degassing , 1190 parts by weight of a coagulate-free dispersion with a solids content of 37.5 % and an average particle size of 132 nm are obtained. The flow time in the DIN beaker (2 mm nozzle) is 75 s.

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Example 14 Polyvinyl chloride latex

In a stainless steel autoclave with anchor stirrer will

3000 parts by weight of distilled water

7.5 parts by weight of an alkyl monosulfonate with

12 to 14 carbon atoms, 6 parts by weight of azo-diisobutyric acid (N, N ¹ , N ¹ -tris-2-hydroxyethyl) amidine and 10 parts by weight of acetic acid

submitted. The autoclave is evacuated, twice at 3 bar Purged nitrogen and evacuated again. In the autoclave are now

1500 parts by weight of vinyl chloride

pumped and the internal temperature brought to 65 ° C. This temperature is held for 12 hours. The initial pressure was 13 bar and the pressure at the end of the polymerization 4 bar.

After degassing, 4175 parts by weight of coagulate-free material are obtained Latex with a particle size of 180 nm. The polymer has an intrinsic viscosity of 0.77 (measured in tetrahydrofuran). The solids content is 29% and the flow time in the DIN cup (2 mm nozzle) 75 s.

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-Vt-

Example 15 Polyvinyl acetate latex

A solution is prepared in a three-necked flask

2) 12.8 parts by weight of polyvinyl alcohol

in 125 parts by weight of distilled water

In the heated to 68 C solution is dripped within of 3 1/2 hours at the same time

1 . A solution from

0.35 part by weight of azo-di-isobutyric acid (N, N'-bis-2-hydroxiethyl) -amidine

in 40 parts by weight of distilled water and 0.8 parts by weight of acetic acid

2. 191 parts by weight of vinyl acetate

During the dropping in, the temperature is kept constant at 68 ° C. The mixture is then stirred for a further 3 1/2 hours at 68 ° C. and a solution of is then added dropwise over the course of 15 minutes

0.05 parts by weight of azo-di-isobutyric acid (N, N ¹ - bis-2-hydroxyethyl) amidine in 10 parts by weight of distilled water

a. The mixture is stirred at 90 ° C. for 45 minutes.

2) Partially saponified polyvinyl acetate (degree of hydrolysis 88%)

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After degassing, 350 parts by weight of a highly viscous dispersion with a solids content of 51% are obtained. The mean particle size is 260 nm.

Example 16 According to Example 15, an initiator is used

equivalent amount of azo-di-isobutyric acid (N, N *, N ¹ -tris-

2-hydroxyethyl amidine

used.

There are 342 parts by weight of a highly viscous dispersion with a solids content of 48% and a particle size of 245 nm obtained.

Example 17 Polychloroprene latex

Be in a three-necked flask

120 parts by weight of distilled water

5 parts by weight sodium salt of a disproportionate

Abietic acid and 0.6 part by weight sodium hydroxide

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submitted. After purging with nitrogen at room temperature for 30 minutes

100 parts by weight of a chloroprene stabilized with 180 ppm phenothiazine

stirred in. The contents of the flask are heated to 64 ° C. with continued nitrogen flushing
Hours a solution of

bring the contents of the flask to 64 C and then drip within

2.5 parts by weight of azo-di-isobutyric acid (N, N ¹ -bis-2-hydroxiethyl) -amidine in 100 parts by weight of distilled water.

The mixture is subsequently stirred at 64 ° C. for 3 hours. The not implemented Chloroprene is removed by steam distillation.

310 parts by weight of a stable dispersion with a solids content of 25.5% and an average solids content are obtained Particle size of 185 nm.

Example 18

According to Example 17, an equivalent amount of azo-di-isobutyric acid- (Ν, Ν ¹ , N'-tris-2-hydroxiethyl) -amidine is used as initiator.

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After removing the unreacted chloroprene by steam distillation, 290 parts by weight of a are obtained coagulate-free dispersion with a solids content of 27% and an average particle size of 170 nm.

Example 19

Styrene-butadiene latex

Be in a stainless steel autoclave with an anchor stirrer

2700 parts by weight of distilled water 7o parts by weight of a disproportionated sodium salt

Abietic acid 7.5 parts by weight of n-dodecyl mercaptan

6 parts by weight of azo-di-isobutyric acid- (N, N ¹ -bis-2-hydroxiethyl) -amidine

submitted. The autoclave is evacuated, twice at 3 bar Purged nitrogen, evacuated again and then successively

435 parts by weight of styrene
^{un (} i 1065 parts by weight of butadiene

pumped in. At a stirrer speed of 150 rpm. will the contents are heated to 65 ° C, the pressure being 10.5 bar

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and kept this temperature for 10 hours. The pressure is now 8.0 bar. After the reaction has ended, a solution of

1 part by weight hydroquinone
in 50 parts by weight of distilled water

depressed.

After degassing, 3450 parts by weight of a coagulate-free one are obtained Latex with a solids content of 33% and an average particle size of 190 nm. The flow time in DIN cup (2 mm nozzle) is 130 s.

Bulk and solution polymerization (Example 20-26) Example 20
A solution of

0.6 part by weight of azo-di-isobutyric acid (N, N ¹ , N'-tris-2-hydroxiethyl) -amidine in 30 parts by weight of styrene

to remove the oxygen in the air 3 minutes with nitrogen fumigated. After the sealed tube has melted, it is heated to 75 ° C. for 8 hours.

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The polymerized content is dissolved in 300 parts by weight of tetrahydrofuran and then precipitated with 10 times the amount by weight of methanol. After vacuum drying at 50 ⁰ C 17 parts by weight are obtained of purified polymer.

Limiting viscosity number (measured in tetrahydrofuran): 0.49

leave over the built-in terminal hydroxyl groups the polymers crosslink with di- and polycyanates.

2 parts by weight of the polystyrene obtained according to Example 20 with terminal hydroxyl groups are in 18 parts by weight dissolved in anhydrous chlorobenzene. The solution is in the presence of 0.05 parts by weight of tin (II) octoate with 0.2 parts by weight Crosslinked hexamethylene diisocyanate.

After standing for 24 hours at room temperature, a cross-linked gel has formed. A film poured onto glass immediately after mixing is also crosslinked after drying out for 24 hours.

Example 21

Following the same procedure as in Example 20, a solution of

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0.6 parts by weight of azo-di-isobutyric acid (N, N ¹ , N ¹ -

tris-2-hydroxiethyl amidine in 30 parts by weight of methyl methacrylate

polymerized. After the reprecipitation, 19 g of polymer are obtained obtained with an intrinsic viscosity in tetrahydrofuran of 0.45.

Example 22

A solution is extracted in a three-necked flask with a thermometer, reflux condenser and nitrogen gas supply

30 parts by weight of acrylonitrile

70 parts by weight of dimethylformamide

and 0.3 part by weight of azo-di-isobutyric acid- (N, N'-bis-2-

hydroxiethyl) amidine

Stirred at 80 ° C. for 6 hours. The resulting highly viscous solution is precipitated in 1000 parts by weight of water and dried at 50 ° C. in a vacuum.

15 parts by weight of polymer with an intrinsic viscosity (measured in dimethylformamide) of 0.58 are obtained.

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Example 23

According to Example 22, a solution is made

30 parts by weight of vinyl acetate 70 parts by weight of tert-butanol 0.3 parts by weight of azo-di-isobutyric acid- (N, N'-bis-

2-hydroxiethyl amidine and 2 parts by weight of acetic acid

Stirred at 80 ^° C. for 6 hours. After the highly viscous solution has been precipitated in 1000 parts by weight of water, 13 parts by weight of polymer having an intrinsic viscosity (measured in dimethylformamide) of 0.35 are obtained after drying.

Example 24

Be in a three-necked flask

500 parts by weight of distilled water

submitted. With ongoing nitrogen flushing, the heated to an internal temperature of 70 C and then metered in evenly within 2 hours:

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841033

a) 100 parts by weight of acrylonitrile

b) A solution of

0.5 part by weight of azo-di-isobutyric acid- (Ν, Ν'-bis-2-hydroxiethyl) -amidine

in 50 parts by weight of distilled water

After the end of the dropwise addition, the mixture is maintained at 70 ° C. for a further 2 hours stirred. The precipitated polyacrylonitrile is filtered off with suction, washed well with water and dried at 50.degree.

75 parts by weight of polymer are obtained.

Example 25

Under the same experimental conditions as in the example, 0.6 parts by weight of azo-di-isobutyric acid are used as initiator (N, N'-bis-2-hydroxipropyl) -amidine is used.

62 parts by weight of polymer are obtained.

Example 26

As in Example 20, a mixture of 22.5 parts of styrene and 7.5 parts of acrylonitrile in the presence of 0.15 parts

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Azo-di-isobutyric acid- (N, N'-bis-2-hydroxiethyl) -amidine polymerized. Instead of tetrahydrofuran, dimethylformamide is used as the solvent for the copolymer used. After vacuum drying, 19 parts of purified copolymer made from 72% styrene and 28% Acrylonitrile units obtained which, measured in dimethylformamide, have an intrinsic viscosity of 0.86.

Example 27

A mixture of 45 parts of styrene and 55 parts of n-butyl acrylate, 400 parts of chlorobenzene and 2 parts of azo-diisobutyric acid- (N, N'-bis-3-hydroxibutyl) -amidine are polymerized as in Example 22 but at 75 ° C. for 6 hours . The resulting copolymer is precipitated from its chlorobenzene solution with 1500 parts of methanol and dried at 50 ° C. in vacuo. 65 parts of copolymer consisting of 49% styrene and 51 % n-butyl acrylate units with an intrinsic viscosity (measured by dimethylformamide) of 0.72 are obtained.

Crosslinking of the copolymer via the built-in OH groups

2 parts of the copolymer, dissolved in 8 parts of anhydrous chlorobenzene, are mixed with 0.05 parts of tin (II) octoate

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and 0.2 parts of isophorone diisocyanate mixed and of films of this solution were drawn onto glass. After 24 hours at room temperature, the films are crosslinked and can can no longer be dissolved by chlorobenzene.

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Claims (4)

Claims Process for the preparation of aqueous plastic dispersions from polymers of polymerized Units of at least one olefinically unsaturated polymerizable monomer by emulsion polymerization in the presence of water-soluble polymerization initiators, characterized in that as Polymerization initiators azo-di-isobutyric acid (Ν, Ν'-hydroxyalkyl) amidines of formula (I) is used, HO-R-N ^^ CH ₃ , 3 ^ N-R- OH HO-R'-N ^ ^ C-C-N = I.
CH ₃ CH ₃ "^ N-R ' -OH X X in which R and R ^{1 represent} linear or branched alkylene radicals having 2 to 4 carbon atoms and X represents hydrogen or R'-OH. 2. The method according to claim 1, characterized in that that the polymerization initiator wholly or partially as a salt of azo-di-isobutyric acid (Ν, Ν'-hydroxialkyl) -amidine of the formula (I) and saturated or monoolefinically unsaturated carbon or sulfone acids is used. Le A 19 058 0300U / 0193 3. The method according to claim 2, characterized in that the monoolefinically unsaturated carboxylic acids Acrylic acid, methacrylic acid, itaconic acid, itaconic acid half-ester or maleic acid half-ester, respectively with 1-18 carbon atoms in the alcohol residue. 4. Use of the dispersions obtained according to claims 1-3 as aqueous coating agents in combination with phenoplasts or aminoplasts or in the production of coating agents. Le A 19 058 0300U / 0193